TECHNICAL FIELD
[0001] The present invention relates to a bonding wire, particularly, a metal-coated Al
bonding wire in which a coating layer is formed on the surface of an Al core wire.
BACKGROUND ART
[0002] In a semiconductor device, electrodes formed on a semiconductor element are connected
with lead frames or electrodes on a substrate using a bonding wire. As for a material
of the bonding wire, gold (Au) and copper (Cu) are used for an integrated circuit
semiconductor device such as an ultra-LSI, while aluminum (Al) is mainly used for
a power semiconductor device. For example, Patent Literature 1 discloses an example
in which an aluminum bonding wire (hereinafter referred to as "Al bonding wire") with
a diameter of 300 µm is used in a power semiconductor module. In a power semiconductor
device using an Al bonding wire, a wedge bonding is used as a bonding process for
both of the connection with electrodes on semiconductor element and the connection
with lead frames or electrodes on substrate.
[0003] An Al bonding wire is inexpensive compared to an Au bonding wire, but is prone to
be oxidized and deteriorate in high humidity. Thus, the wire needs a vacuum package
or a package with inert gas sealed inside, which is expensive, and cannot be adapted
to an inexpensive resin package. Further, a power semiconductor device using an Al
bonding wire is often used as a semiconductor device for large power equipment such
as air conditioner and photovoltaic power generation system, and for automotive. In
these semiconductor devices, the bonded parts of Al bonding wire are exposed to high
temperatures of 100 to 300°C. Since an Al bonding wire composed only of high purity
Al tends to soften in such a high temperature environment, it is difficult to use
such Al bonding wire in a high temperature environment. Patent Literature 2 describes
a method of manufacturing a gold-coated aluminum bonding wire. The Literature disclosed
that the gold-coated aluminum bonding wire can be adapted to an inexpensive resin
package, and ball bonding is made possible even though the wire is aluminum wire.
[0004] In manufacture of a bonding wire, a wire drawing process using dies is performed.
The same applies to Al or Al alloy bonding wires. When drawing an Al or Al alloy bonding
wire using dies, abrasion powders of aluminum may be generated due to the abrasion
of Al or Al alloy caused by the dies because Al and Al alloy are soft. This abrasion
powder may adversely generate flaws on the surface of wire to be drawn thereafter,
and cause on-axis eccentricity. As described in Patent Literature 2, since Au is harder
than Al, an Au coating on the surface of Al wire can prevent the generation of abrasion
powder during wire drawing.
[0005] Patent Literature 3 discloses a bonding wire including a core wire of Al or Al alloy,
and a coating layer A coating the core wire, in which the metal constituting the coating
layer A is Mo, Nb, Cr, Co, Ti, Zr, Ta, Fe or an alloy thereof. The coating layer A
prevents the generation of the abrasion powder due to scraping the wire during the
wire drawing using dies. Furthermore, the coating metal such as Mo prevent the Al
core wire from corrosion even when used to an inexpensive resin package, whereas an
Au coating does not prevent the Al core wire from corrosion.
RELATED ART REFERENCE
Patent Literature
SUMMARY OF INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION
[0007] Even for the semiconductor devices using an Al bonding wire including a coating layer
like those described in Patent Literatures 1 and 2, sufficient bonding reliability
of the bonded parts of the bonding wire was sometimes not achieved under a high temperature
state where the semiconductor device was operated.
[0008] An object of the present invention is to provide a metal-coated Al bonding wire which
achieves sufficient bonding reliability of bonded parts of the bonding wire under
a high temperature state where a semiconductor device using the metal-coated Al bonding
wire is operated.
MEANS FOR SOLVING PROBLEM
[0009] That is, the summary of the present invention is as follows.
- [1] A bonding wire comprising:
a core wire of Al or Al alloy; and
a coating layer of Ag, Au or an alloy containing them formed on an outer periphery
of the core wire, wherein
when measuring crystal orientations on a cross-section of the core wire in a direction
perpendicular to a wire axis of the bonding wire, a crystal orientation <111> angled
at 15 degrees or less to a wire longitudinal direction has a proportion of 30 to 90%
among crystal orientations in the wire longitudinal direction.
- [2] The bonding wire according to [1], wherein a surface roughness of the wire is
2 µm or less in terms of Rz.
- [3] The bonding wire according to [1] or [2], wherein a thickness of the coating layer
is 1 to 100 nm.
- [4] The bonding wire according to any one of [1] to [3], wherein a wire diameter is
50 to 600 µm.
EFFECT OF THE INVENTION
[0010] The bonding wire of the present invention includes a core wire of Al or Al alloy,
and a coating layer of Ag, Au or an alloy containing them formed on the outer periphery
of the core wire, and is characterized in that when measuring crystal orientations
on a cross-section of the core wire in a direction perpendicular to a wire axis of
the bonding wire, a crystal orientation <111> angled at 15 degrees or less to a wire
longitudinal direction has a proportion of 30 to 90% among crystal orientations in
the wire longitudinal direction. Thus, sufficient bonding reliability of the bonded
parts of the bonding wire can be ensured under a high temperature state where a semiconductor
device using the bonding wire is operated.
EMBODIMENT FOR CARRYING OUT THE INVENTION
[0011] The present invention is directed to a metal-coated Al bonding wire including a core
wire of Al or Al alloy (hereinafter, may also be simply referred to as an "Al core
wire") and a coating layer of Ag, Au or an alloy containing them (hereinafter, may
also be simply referred to as "Ag/Au coating layer") formed on the outer periphery
of the core wire.
[0012] The bonding wire of the present invention includes a core wire of Al or Al alloy
as a core wire. In the case where Al is used, the Al content of the core wire is 99.9%
by mass or more. In the case where Al alloy is used, an alloy such as Al-Si, Al-Fe
or the like is used and the Al content thereof is 90% by mass or more. The components
constituting the core wire includes inevitable impurities in addition to Al or the
components constituting the Al alloy described above.
[0013] The heat treatment during the manufacture of the bonding wire may form a diffusion
region between the metal of the coating layer and the metal of the core wire at the
boundary between the coating layer and the core wire. In the diffusion region, the
content of the metal of the coating layer gradually decreases and the content of the
metal of the core wire gradually increases from the coating layer side toward the
center of the wire. In the present invention, the position at which the content of
the metal of the core wire is 50at% is defined as the boundary between the coating
layer and the core wire. When the diffusion region is formed at the boundary between
the core wire and the coating layer, the core wire contains the components of the
coating layer in the diffusion region therein, and the content thereof is 50at% or
less.
[0014] The component constituting the coating layer includes Ag, Au or an alloy containing
them, and further includes inevitable impurities. When using Ag, Au or an alloy containing
them for the component constituting the coating layer, good bonding property and high
bonding strength can be achieved. In the case where an alloy containing Ag or Au is
used, the content of Ag or Au in the alloy is 50% by mass or more, and Al may be contained
as the alloy component. In the case where the diffusion region is formed at the boundary
between the core wire and the coating layer, the coating layer contains the component
of the core wire in the diffusion region therein, and the content thereof is 50at%
or less.
[0015] The invention described in Patent Literature 1 using an Au-coated Al bonding wire
can be applied to a low-cost resin package, and ball bonding is made possible even
though the wire is an Al wire. The invention described in Patent Literature 2 using
an Al bonding wire with a coating layer of Mo or the like does not generate abrasion
powder due to scraping during wire drawing using dies, and prevents the Al core wire
from corrosion even when used to an inexpensive resin package.
[0016] As for the semiconductor device using an Ag- or Au-coated Al bonding wire, when the
semiconductor device was operated for a long time under a high temperature state,
there was observed a phenomenon in which the bonding strength of the bonded parts
of the bonding wire decreased. In other words, it was found that sufficient bonding
reliability cannot be achieved. According to the observation of the cross-section
of the bonding wire in the semiconductor device after long-term operation under a
high temperature, it was found that recrystallization occurred and the crystal grain
size increased due to a high temperature environment, and a crystal orientation <111>
proportion, which will be described later, was reduced. It was therefore inferred
that the wire strength was reduced as compared to the initial strength, resulting
in an occurrence of peeling phenomenon at the bonding interface and a decrease in
the reliability of the bonded parts.
[0017] In contrast, the metal-coated Al bonding wire of the present invention includes an
Ag/Au coating layer formed on the outer periphery of the Al core wire, and is characterized
in that when measuring crystal orientations on a cross-section of the core wire in
a direction perpendicular to a wire axis of the bonding wire, a crystal orientation
<111> angled at 15 degrees or less to a wire longitudinal direction has a proportion
of 30 to 90% among crystal orientations in the wire longitudinal direction. Hereinafter,
such proportion of a crystal orientation <111> may also be simply referred to as "crystal
orientation <111> proportion". Thus, even when the semiconductor device is continuously
operated for a long time under a high temperature environment, it is possible to ensure
the reliability of the bonded parts in the semiconductor device after long-term operation
under a high temperature. A detailed description will next be given.
[0018] There will be described an evaluation test of reliability of the bonded parts after
a high-temperature long-term hysteresis.
[0019] As a metal-coated Al bonding wire, an Au-coated Al bonding wire and an Ag-coated
Al bonding wire were prepared. The coating thickness of the coating layer was 50 nm
for each wire. The wire diameter after wire drawing is 200 µm. In the middle of the
wire drawing process, some of the wires were subjected to a heat treatment. When the
heat treatment was performed, two types of cooling conditions had been employed including
slow cooling and quenching. The wires after being drawn were subjected to a thermal
refining heat treatment. By varying the condition of heat treatment in the middle
of wire drawing and the condition of thermal refining heat treatment after wire drawing,
the crystal orientation <111> proportion was variously changed.
[0020] In the semiconductor device, both the first bonded part between the semiconductor
chip and the bonding wire and the second bonded part between the external terminal
and the bonding wire utilized wedge bonding.
[0021] The high-temperature long-term hysteresis was performed by power cycle test. The
power cycle test involves repeatedly heating and cooling the semiconductor device
in which the Al bonding wires are bonded. Specifically, the semiconductor device is
heated over 2 seconds until the temperature of the bonded parts of the bonding wires
in the semiconductor device becomes 140°C, and then is cooled over 5 seconds until
the temperature of the bonded parts becomes 30°C. This heating and cooling cycle is
repeated 200,000 times.
[0022] After performing the high-temperature long-term hysteresis as noted above, the bonding
shear strength of the first bonded part was measured to evaluate the reliability of
the bonded part. As a result, when the crystal orientation <111> proportion falls
within a range of 30 to 90% (condition of the present invention), both the Au-coated
wire and the Ag-coated wire had a bonding shear strength of 90% or more compared to
the initial strength, so that the sufficient reliability of the bonded parts could
be ensured. On the other hand, when the crystal orientation <111> proportion was out
of the condition of the present invention as noted above, the bonding shear strength
was less than 50% compared to the initial strength, and the reliability of the bonded
parts was insufficient.
<<Crystal orientation <111> proportion of wire>>
[0023] When measuring crystal orientations on a cross-section of the core wire in a direction
perpendicular to a wire axis of the bonding wire of the present invention, a crystal
orientation <111> angled at 15 degrees or less to a wire longitudinal direction has
a proportion of 30 to 90% among crystal orientations in the wire longitudinal direction.
Herein, the cross-section of the core wire in a direction perpendicular to a wire
axis means a cross-section (C-section) perpendicular to the longitudinal direction
of the bonding wire. For the measurement of the crystal orientation <111> proportion,
EBSD (Electron Back Scatter Diffraction Patterns) can be used. The crystal orientation
<111> proportion can be calculated by inspecting the cross-section of the core wire
in a direction perpendicular to a wire axis (cross-section perpendicular to the longitudinal
direction of the bonding wire) as an inspection surface, and using an analysis software
dedicated to the measuring device. Regarding the calculation method of the orientation
proportion, the crystal orientation <111> proportion is defined as the areal percentage
of crystal orientation <111> which is calculated by using, as a population, only the
area where crystal orientation can be identified with a certain reliability within
the measurement area. In the process of determining the orientation proportion, there
is excluded a portion where crystal orientation cannot be measured or a portion where
the reliability of orientation analysis is low even when crystal orientation can be
measured.
[0024] If the crystal <111> orientation proportion is 90% or less, recrystallization due
to the thermal refining heat treatment during wire drawing proceeds moderately, and
the wire is softened. Thus, it is possible to prevent the wire from: chip cracking
during bonding; having a lower bonding property of the bonded parts; having a decreased
reliability during a high-temperature long-term use, and the like. On the other hand,
the crystal orientation <111> proportion of less than 30% indicates that the recrystallization
of the wire has proceeded too much. Thus, the reliability of the bonded parts is reduced,
and the reliability during a high-temperature long-term use is also reduced.
[0025] By performing the heat treatment during wire drawing, and quenching after heat treatment
in combination with the appropriate coating thickness and the thermal refining heat
treatment after wire drawing, the crystal orientation <111> proportion in a cross-section
perpendicular to the longitudinal direction of the wire can be adjusted to 30 to 90%.
The crystal orientation <111> proportion is preferably 40% or more, and more preferably
50% or more. The crystal orientation <111> proportion is also preferably 80% or less,
and more preferably 70% or less.
«Surface roughness of wire»
[0026] In the present invention, it is preferable that the surface roughness of the wire
is 2 µm or less in terms of Rz. By forming a coating layer of Ag, Au or an alloy containing
them on the surface of the wire and then drawing the wire so that the thickness of
the coating layer is 1 nm or more, the surface roughness Rz can be adjusted to 2 µm
or less. The surface roughness Rz of 2 µm or less can improve the bonding property
to electrodes at the time of bonding. Surface roughness Rz is the maximum height Rz
defined in JIS B 0601-2001. This can be evaluated by the roughness in the longitudinal
direction of the wire by a non-contact ultra-deep shape measuring microscope.
<<Thickness of coating layer>>
[0027] In the metal-coated Al bonding wire of the present invention, the thickness of the
coating layer is preferably 1 to 100 nm. It can thus prevent a deterioration of die
abrasion without generating abrasion powder due to scraping during wire drawing using
dies. In addition, it is possible to sufficiently exhibit the effect of reducing the
surface roughness Rz of the wire.
[0028] If the thickness of the coating layer is too thin, it is impossible to exert an effect
of the coating layer formed, thereby impairing die abrasion. Thus, the surface roughness
of the wire deteriorates, and as a result, the bonding property to electrodes at the
time of bonding deteriorates. When the thickness of the coating layer is 1 nm or more,
the function and effects of the coating layer of the present invention can be exhibited.
The thickness of the coating layer is more preferably 10 nm or more, and further preferably
20 nm or more.
[0029] On the other hand, if the thickness of the coating layer is too thick, the friction
during wire drawing is small, and the processing degree of the Al core wire becomes
small. Thus, the orientation <111> proportion of the wire decreases. When the thickness
of the coating layer is 100 nm or less, the function and effects of the coating layer
of the present invention can be exhibited. The thickness of the coating layer is more
preferably 40 nm or less, and further preferably 30 nm or less.
[0030] When the wire diameter to be described later is defined as D (µm), the thickness
d (nm) of the coating layer is preferably more than 0.02D, more preferably 0.03D or
more, 0.04D or more, or 0.05D or more. Further, the thickness d (nm) of the coating
layer is preferably 0.2D or less, more preferably 0.18D or less, 0.16D or less, or
0.15 D or less. In particular, when the wire diameter D (µm) and the thickness d (nm)
of the coating layer satisfy the relation of 0.05D ≤ d ≤ 0.15D, the above-mentioned
effects due to the formation of the coating layer can be remarkably achieved.
<<Wire diameter >>
[0031] In the present invention, the diameter of the bonding wire is preferably 50 to 600
µm. Wires with diameter of 50 µm or more are generally used for power system devices
due to a large current flow. Wires with diameter exceeding 600 µm are difficult to
handle and no wire bonders are available for them. Thus, wires with diameter of 600
µm or less are used.
<<Components of wire>>
[0032] For the Al bonding wire of the present invention, any of pure Al and an Al alloy
can be appropriately applied. The Al alloy may contain an additive element such as
Fe, Si, or the like, and examples thereof may include an Al-Fe alloy and an Al-Si
alloy. The Al content thereof is preferably 95% by mass or more, 96% by mass or more,
97% by mass or more, 98% by mass or more, or 98.5% by mass or more. Preferable examples
of the Al alloy may include an alloy of Al-0.5% by mass Fe and an alloy of Al-1% by
mass Si.
<<Method for manufacturing bonding wire>>
[0033] First, in accordance with the composition of the core wire, a high-purity Al (purity
of 99.99% or higher) and a raw material for an additive element are weighed as starting
materials. After that, the starting materials are heated and melted under high vacuum
or in an inert atmosphere such as nitrogen or argon, thus obtaining an ingot containing
predetermined components with the balance containing Al and inevitable impurities.
The ingot is then drawn using metal dies to form the core wire with a finally required
diameter.
[0034] As a method of forming the coating layer on the surface of the core wire, electrolytic
plating, electroless plating, vapor deposition, or the like can be used. From the
viewpoint of productivity, it is industrially most preferable to use electrolytic
or electroless plating. As to the step of applying the coating layer on the surface
of the core wire, it is most preferable to coat it while it is still an ingot. This
may also be achieved by drawing the ingot to form an intermediate core wire with a
predetermined wire diameter, coating it with the coating layer at a stage after the
Al abrasion powder is formed with dies, and then drawing the resultant to be a wire
with a final wire diameter.
[0035] In manufacturing the bonding wire of the present invention, in addition to the rolling
and wire drawing as the common procedure, the wire is subjected to a heat treatment
and a subsequent quenching treatment in the middle of wire drawing. The heat treatment
can be performed at a stage when the wire diameter is about 1 mm. The condition of
the heat treatment during wire drawing is preferably 600 to 640°C for 2 to 3 hours.
The quenching treatment after the heat treatment is performed in water. By performing
such a heat treatment and subsequent quenching during wire drawing while also maintaining
the film thickness of the coating layer of the wire not too thick, the crystal orientation
<111> proportion after the thermal refining heat treatment described below can be
adjusted within the scope of the present invention.
[0036] When the heat treatment is not conducted, the crystal orientation <111> proportion
exceeds the upper limit after the thermal refining heat treatment described below.
In particular, this is remarkable when the coating layer is thin. Further, if the
wire is cooled slowly even when the heat treatment is conducted or the heat treatment
is performed at too high temperature, the crystal orientation <111> proportion is
below the lower limit after the thermal refining heat treatment described below. In
particular, this is remarkable when the coating layer is thick.
[0037] The thermal refining heat treatment is performed during and/or after the wire drawing.
It is possible to reduce the crystal orientation <111> proportion by increasing the
temperature of the thermal refining heat treatment and extending the time thereof.
The condition of the thermal refining heat treatment can be determined within a range
of 250 to 350°C for the heat treatment temperature and within a range of 5 to 15 seconds
for the heat treatment time so as to realize a preferable crystal orientation <111>
proportion.
Examples
[0038] As raw materials of the bonding wire, specifically, as Al used for a core wire, Au
and Ag used for a coating layer, materials with a purity of 99.99% by mass or more
were prepared separately. An ingot was forged by heating and melting Al, and a coating
layer was formed on a surface of the wire using an electrolytic plating method. After
that, while wire drawing was performed, a heat treatment during the wire drawing and
a thermal refining heat treatment after the wire drawing were performed, thus manufacturing
a bonding wire with a final wire diameter shown in Table 1. The coating layer was
controlled to have the thickness described in Examples.
[0039] As for the heat treatment during the wire drawing, the heat treatment was performed
at a stage where the wire diameter became 800 µm. In Working Examples, the heat treatment
was performed at 620°C for 3 hours with quenching (water cooling). In Comparative
Examples 1 to 4, slow cooling (air cooling) was adopted as the cooling condition.
In Comparative Examples 5 and 6, no heat treatment was performed. Further, the conditions
of the thermal refining heat treatment after the wire drawing were as follows. The
standard condition was within a range of 270±10°C for 10 seconds. As to Working Example
Nos. 19 and 20 (the thickness of the coating layer is greater than those of the preferable
range of the present invention), the condition of the thermal refining heat treatment
was lower in temperature than the standard condition, in order to adjust the crystal
orientation <111> proportion.
[0040] The thickness of the coating layer in the resulting bonding wire was measured by
ICP analysis to obtain an average film thickness. The metal type and thickness of
the coating layer is shown in Table 1.
[0041] The measurement of the crystal orientation <111> proportion (the orientation proportion
of crystal in which a crystal orientation <111> is angled at 15 degrees or less to
a wire longitudinal direction in a cross-section perpendicular to the wire longitudinal
direction) was performed by measuring with EBSD on a cross-section perpendicular to
the longitudinal direction of the bonding wire, and calculating the crystal orientation
<111> proportion in the above-described procedure using the analysis software dedicated
to the measuring device.
[0042] The surface roughness Rz of the wire was evaluated as the longitudinal roughness
of the wire with a non-contact ultra-deep shape measuring microscope in accordance
with the provisions of JIS B 0601-2001.
[0043] The die abrasion was evaluated by measuring the amount of increase in wire diameter.
After drawing a wire of predetermined length, the wire diameter was measured to confirm
how the actual wire diameter was increased compared to the target wire diameter. The
die abrasion was evaluated according to the degree of increase in the wire diameter
and was marked with symbols of "double circle", "circle" and "triangle" in ascending
order in terms of the degree of increase in the wire diameter.
[0044] The bonding wire was bonded using a commercially available wedge bonder. As the sample
for evaluation, a copper substrate having a SiC chip mounted thereon was used. Onto
the SiC chip, Titanium, nickel and aluminum were deposited from the SiC chip side
in advance, and the thicknesses thereof were 0.1, 2 and 4 µm, respectively.
[0045] The bonding property of the bonding wire was evaluated by the wedge bondability.
Specifically, its shear strength was evaluated. As for the shear strength, a shear
strain was applied to the bonding wire in a state of being wedge bonded in a direction
perpendicular to the wire, and the maximum strength that would cause it to fracture
was recorded. In the evaluation, the shear strength being 95% or more of the initial
bonding strength was marked with a symbol of "double circle", being 90% to 95% of
the initial bonding strength was marked with a symbol of "circle", and being 70% to
90% of the initial bonding strength was marked with a symbol of "triangle", and any
case of which were determined to be acceptable. On the other hand, the shear strength
being less than 70% of the initial bonding strength was determined to be unacceptable.
[0046] The high-temperature long-term hysteresis was performed by a power cycle test. The
power cycle test involved repeatedly heating and cooling the semiconductor device
in which an Al bonding wire had been bonded. Specifically, the semiconductor device
was heated over 2 seconds until the temperature of the bonded parts of the bonding
wires in the semiconductor device became 140°C, and then was cooled over 5 seconds
until the temperature of the bonded parts became 30°C. This heating and cooling cycle
was repeated 200,000 times.
[0047] After performing the high-temperature long-term hysteresis, the bonding shear strength
of the first bonded part was measured to evaluate the reliability of the bonded part.
The shear strength was measured as a comparison with the initial shear strength of
the bonded part. In the evaluation, the shear strength being 95% or more of the initial
bonding strength was marked with a symbol of "double circle", being 90% to 95% of
the initial bonding strength was marked with a symbol of "circle", being 70% to 90%
of the initial bonding strength was marked with a symbol of "triangle", and being
less than 70% of the initial bonding strength was marked with a symbol of "cross"
in the column "reliability test" in Table 1. The evaluations of "double circle" and
"circle" were determined to be acceptable and the others were determined to be unacceptable.
[Table 1]
[0048]
(Table 1 )
|
No. |
Wire Specification |
Wire Crystal Texture |
Wire Propeties |
Remarks (Heat treatment conditions) |
Wire diameter (µm) |
Thickness of coating layer (nm) |
Orientation <111> proportion (%) |
Surface ro ugh ne ss Rz (µm) |
Die abrasion |
Bonding property |
Reliability test |
Ag |
Au |
Working Example |
1 |
50 |
10 |
0 |
33 |
1.5 |
○ |
○ |
○ |
|
2 |
50 |
5 |
0 |
50 |
1.8 |
⊚ |
⊚ |
⊚ |
|
3 |
50 |
1 |
0 |
86 |
1.1 |
○ |
○ |
○ |
|
4 |
50 |
0 |
10 |
31 |
1.7 |
○ |
○ |
○ |
|
5 |
50 |
0 |
5 |
53 |
1.1 |
⊚ |
⊚ |
⊚ |
|
6 |
50 |
0 |
1 |
90 |
1.3 |
○ |
○ |
○ |
|
7 |
200 |
40 |
0 |
32 |
1.8 |
○ |
○ |
○ |
|
8 |
200 |
20 |
0 |
51 |
1.0 |
⊚ |
⊚ |
⊚ |
|
9 |
200 |
1 |
0 |
89 |
1.7 |
○ |
○ |
○ |
|
10 |
200 |
0 |
40 |
31 |
1.7 |
○ |
○ |
○ |
|
11 |
200 |
0 |
20 |
52 |
1.3 |
⊚ |
⊚ |
⊚ |
|
12 |
200 |
0 |
1 |
87 |
1.8 |
○ |
○ |
○ |
|
13 |
600 |
100 |
0 |
32 |
1.4 |
○ |
○ |
○ |
|
14 |
600 |
50 |
0 |
52 |
1.7 |
⊚ |
⊚ |
⊚ |
|
15 |
600 |
1 |
0 |
88 |
1.6 |
○ |
○ |
○ |
|
16 |
600 |
0 |
100 |
33 |
1.8 |
○ |
○ |
○ |
|
17 |
600 |
0 |
50 |
51 |
1.1 |
⊚ |
⊚ |
⊚ |
|
18 |
600 |
0 |
1 |
86 |
1.9 |
○ |
○ |
○ |
|
19 |
200 |
120 |
0 |
32 |
1.5 |
○ |
△ |
○ |
Termal refining heat treatment_low temperature |
20 |
200 |
0 |
120 |
34 |
1.7 |
○ |
△ |
○ |
ditto |
21 |
200 |
0.5 |
0 |
88 |
2.3 |
△ |
△ |
○ |
|
22 |
200 |
0 |
0.5 |
79 |
2.5 |
△ |
△ |
○ |
|
Comparative Example |
1 |
200 |
120 |
0 |
29 |
1.5 |
○ |
△ |
△ |
Slow cooling after heat treatment during wire drawing |
2 |
200 |
0 |
120 |
28 |
1.7 |
O |
△ |
△ |
ditto |
3 |
200 |
100 |
0 |
26 |
1.2 |
△ |
△ |
× |
ditto |
4 |
200 |
0 |
100 |
27 |
1.4 |
△ |
△ |
× |
ditto |
5 |
200 |
1 |
0 |
93 |
1.8 |
△ |
△ |
× |
No heat treatment during wire drawing |
6 |
200 |
0 |
1 |
91 |
1.9 |
△ |
△ |
× |
ditto |
[0049] The results are shown in Table 1. Values outside the range of the present invention
are underlined.
[0050] All of Working Example Nos. 1 to 22 had the crystal orientation <111> proportion
being within the range of the present invention, and they achieved favorable results
in all of die abrasion, bonding property, and reliability test. In particular, Working
Example Nos. 1 to 18 had the thickness of the coating layer being within the preferable
range of the present invention, and all of them achieved favorable results in the
reliability test. Further, Working Example Nos. 2, 5, 8, 11, 14 and 17 had the thickness
of the coating layer and the crystal orientation <111> proportion being within the
more preferable range of the present invention, and they achieved evaluation of "double
circle" in all of the die abrasion, bonding property, and reliability test.
[0051] Working Example Nos. 19 and 20 had the thickness of the coating layer being thicker
than those under the preferable condition of the present invention. Although the crystal
orientation <111> proportion thereof was within the range of the present invention
by performing the thermal refining heat treatment at a lower temperature than those
under the standard condition, they merely achieved evaluation of "triangle" in the
bonding property.
[0052] As for Working Example Nos. 21 and 22 in which the thickness of the coating layer
was below the preferable lower limit, the evaluation results of die abrasion, surface
properties, and bonding property were "triangle".
[0053] Comparative Example Nos. 1 and 2 had the thickness of the coating layer being thicker
than those under the preferable condition of the present invention, and had the crystal
orientation <111> proportion being out of the lower limit of the range of the present
invention since the thermal refining heat treatment was performed under the standard
condition. As for them, the result of the reliability test was "triangle" (unacceptable),
and the result of the bonding property was "triangle".
[0054] Comparative Example Nos. 3 and 4 had the crystal orientation <111> proportion being
out of the lower limit of the range of the present invention since the cooling condition
after the heat treatment during the wire drawing was slow cooling (air cooling). As
for them, the result of the reliability test was "cross", and both results of the
die abrasion and the bonding property were "triangle".
[0055] Comparative Example Nos. 5 and 6 had the crystal orientation <111> proportion being
out of the upper limit of the range of the present invention since the heat treatment
during the wire drawing was not performed. As for them, the result of the reliability
test was "cross", and both results of the die abrasion and the bonding property were
"triangle".